A variety of metallocenes and other single site-like catalysts have been developed to prepare olefin polymers. Metallocenes are organometallic coordination complexes containing one or more .pi.-bonded moieties (i.e., cyclopentadienyl groups) in association with a metal atom. Catalyst compositions containing metallocenes and other single site-like catalysts are highly useful in the preparation of polyolefins, producing relatively homogeneous copolymers at excellent polymerization rates while allowing one to tailor closely the final properties of the polymer as desired.
Recently, work relating to certain nitrogen-containing, single site-like catalyst precursors has been published. PCT Application No. WO 96/23101 relates to di(imine) metal complexes that are transition metal complexes of bidentate ligands selected from the group consisting of: ##STR2##
wherein said transition metal is selected from the group consisting of Ti, Zr, Sc, V, Cr, a rare earth metal, Fe, Co, Ni, and Pd;
R.sup.2 and R.sup.5 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; PA1 R.sup.3 and R.sup.4 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or R.sup.3 and R.sup.4 taken together are hydrocarbylene or substituted hydrocarbylene to form a carbocyclic ring; PA1 R.sup.44 is hydrocarbyl or substituted hydrocarbyl, and R.sup.28 is hydrogen, hydrocarbyl or substituted hydrocarbyl or R.sup.44 and R.sup.28 taken together form a ring; PA1 R.sup.45 is hydrocarbyl or substituted hydrocarbyl, and R.sup.29 is hydrogen, substituted hydrocarbyl or hydrocarbyl, or R.sup.45 and R.sup.29 taken together form a ring; PA1 each R.sup.30 is independently hydrogen, substituted hydrocarbyl or hydrocarbyl, or two of R.sup.30 taken together form a ring; PA1 each R.sup.31 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; PA1 R.sup.46 and R.sup.47 are each independently hydrocarbyl or substituted hydrocarbyl, provided that the carbon atom bound to the imino nitrogen atom has at least two carbon atoms bound to it; PA1 R.sup.48 and R.sup.49 are each independently hydrogen, hydrocarbyl, or substituted hydrocarbyl; PA1 R.sup.20 and R.sup.23 are independently hydrocarbyl or substituted hydrocarbyl; PA1 R.sup.21 and R.sup.22 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; and PA1 n is 2 or 3; and provided that: PA1 said transition metal also has bonded to it a ligand that may be displaced by or added to the olefin monomer being polymerized; and PA1 when the transition metal is Pd, said bidentate ligand is (V), (VII) or (VIII). PA1 X is a noncoordinating anion; PA1 Ar.sup.1 is an aromatic moiety with n free valencies, or diphenylmethyl; PA1 each Q is --NR.sup.2 R.sup.43 or --CR.sup.9.dbd.NR.sup.3 ; PA1 R.sup.43 is hydrogen or alkyl; PA1 n is 1 or 2; PA1 E is 2-thienyl or 2-furyl; PA1 each R.sup.2 is independently hydrogen, benzyl, substituted benzyl, phenyl or substituted phenyl; PA1 each R.sup.9 is independently hydrogen or hydrocarbyl; and PA1 each R.sup.3 is independently a monovalent aromatic moiety; PA1 m is 1, 2 or 3; PA1 each R.sup.4, R.sup.5, R.sup.6, and R.sup.7 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; PA1 each R.sup.8 is independently hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms; PA1 each R.sup.10 is independently hydrogen, hydrocarbyl or substituted hydrocarbyl; PA1 Ar.sup.2 is an aryl moiety; PA1 R.sup.12, R.sup.13, and R.sup.14 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or an inert functional group; PA1 R.sup.11 and R.sup.15 are each independently hydrocarbyl, substituted hydrocarbyl or an inert functional group whose E.sub.S is about -0.4 or less; PA1 each R.sup.16 and R.sup.17 is independently hydrogen or acyl containing 1 to 20 carbon atoms; PA1 Ar.sup.3 is an aryl moiety; PA1 R.sup.18 and R.sup.19 are each independently hydrogen or hydrocarbyl; PA1 Ar.sup.4 is an aryl moiety; PA1 Ar.sup.5 and Ar.sup.6 are each independently hydrocarbyl; PA1 Ar.sup.7 and Ar.sup.8 are each independently an aryl moiety; PA1 Ar.sup.11 is an aryl moiety; PA1 R.sup.41 is hydrogen or hydrocarbyl; PA1 R.sup.42 is hydrocarbyl or --C(O)--NR.sup.41 --Ar.sup.11 ; PA1 R.sup.44 is aryl; PA1 R.sup.22 and R.sup.23 are each independently phenyl groups substituted by one or more alkoxy groups, each alkoxy group containing 1 to 20 carbon atoms; and PA1 R.sup.24 is alkyl containing 1 to 20 carbon atoms, or an aryl moiety. PA1 M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements; PA1 each L is a monovalent, bivalent, or trivalent anion; PA1 X and Y are each heteroatoms; PA1 Cyclo is a cyclic moiety; PA1 each R.sup.1 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R.sup.1 groups may be joined to form a cyclic moiety; PA1 each R.sup.2 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R.sup.2 groups may be joined to form a cyclic moiety; PA1 Q is a bridging group; PA1 each m is independently an integer from 0 to 5; PA1 n is an integer from 1 to 4; PA1 q is 1 or 2; PA1 and when q is 2, the A groups are optionally connected by a bridging group Z. PA1 M is a metal selected from the group consisting of Group 3 to 13 elements and Lanthanide series elements; PA1 each L is a monovalent, bivalent, or trivalent anion; PA1 X and Y are each heteroatoms; PA1 Cyclo is a cyclic moiety; PA1 each R.sup.1 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R.sup.1 groups may be joined to form a cyclic moiety; PA1 each R.sup.2 is independently a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R.sup.2 groups may be joined to form a cyclic moiety; PA1 Q is a bridging group; PA1 each m is independently an integer from 0 to 5; PA1 n is an integer from 1 to 4; PA1 q is 1 or 2; PA1 and when q is 2, the A groups are optionally connected by a bridging group Z; along with a catalyst composition comprising this catalyst precursor and an activating cocatalyst, as well as a process for the polymerization of olefins, using this catalyst composition. PA1 Cyclo is a cyclic moiety; PA1 each R.sup.1 is a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R.sup.1 groups may be joined to form a cyclic moiety; PA1 each R.sup.2 is a group containing 1 to 50 atoms selected from the group consisting of hydrogen and Group 13 to 17 elements, and two or more adjacent R.sup.2 groups may be joined to form a cyclic moiety; PA1 Q is a bridging group; and PA1 each m is independently an integer from 0 to 5; as well as a catalyst composition comprising this catalyst precursor and an activating cocatalyst, and a process for polymerizing olefins using this catalyst composition. PA1 each R" is a hydrocarbon group containing 1 to 20 carbon atoms and two or more adjacent R" groups may be joined to form an aliphatic or aromatic ring; and PA1 R.sup.3 is hydrogen, a hydrocarbon group containing 1 to 20 carbon atoms optionally substituted with one or more heteroatoms, or a heteroatom optionally substituted with a hydrocarbon group.
Similarly, PCT Application No. WO 97/02298 relates to a process for the polymerization of an olefin, comprising contacting a polymerizable monomer consisting essentially of ethylene, a norbornene or a styrene, with a catalyst system comprising the product of mixing in solution a zerovalent tricoordinate or tetracoordinate nickel compound (II) which has at least one labile ligand, and all ligands are neutral, an acid of the formula HX (IV), and a first compound selected from the group consisting of:
Ar.sup.1 Qn (III); R.sup.8 R.sup.10 N--CR.sup.4 R.sup.5 (CR.sup.6 R.sup.7).sub.m --NR.sup.8 R.sup.10 (V); ##STR3## R.sup.8 S--CR.sup.4 R.sup.5 (CR.sup.6 R.sup.7).sub.m --SR.sup.8 (XXXVII);
wherein:
Ar.sup.9 and Ar.sup.10 are each independently an aryl moiety or --CO.sub.2 R.sup.25, wherein R.sup.25 is alkyl containing 1 to 20 carbon atoms;
PCT Application No. WO 96/33202 relates to a transition metal catalyst containing a pyridine or quinoline moiety and having the formula: ##STR4##
each R is independently selected from hydrogen or C.sub.1 to C.sub.6 alkyl, each R' is independently selected from C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, C.sub.6 to C.sub.16 aryl, halogen, or CF.sub.3, M is titanium, zirconium, or hafnium, each X is independently selected from halogen, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, or ##STR5##
L is X, cyclopentadienyl, C.sub.1 to C.sub.6 alkyl substituted cyclopentadienyl, indenyl, fluorenyl, or ##STR6##
"m" is 0 to 4, and "n" is 1 to 4.
Similarly, Fuhrmann et al., Inorg. Chem., 35:6742-6745 (1996) discloses certain Group 4 metal complexes containing amine, amido, and aminopyridinato ligands such as: ##STR7##
wherein TMS is trimethylsilyl.
An olefin polymerization catalyst composition is described herein having good polymerization activity and productivity. The catalyst composition comprises a heteroatom-containing catalyst precursor having the formula: EQU A.sub.q ML.sub.n
wherein each A has the formula: ##STR8##
The catalyst precursor may be conveniently prepared by reacting an organometal compound with a heteroatom-containing ligand of the formula: ##STR9##
wherein X, Y, Q, Cyclo, R.sup.1, R.sup.2, and m have the meanings stated above.